Methods of making carbon nanotube films, layers, fabrics, ribbons, elements and articles

ABSTRACT

Methods of making carbon nanotube films, layers, fabrics, ribbons, elements and articles are disclosed. Carbon nanotube growth catalyst is applied on to a surface of a substrate. The substrate is subjected to a chemical vapor deposition of a carbon-containing gas to grow a non-woven fabric of carbon nanotubes. Portions of the non-woven fabric are selectively removed according to a defined pattern to create the article. A non-woven fabric of carbon nanotubes may be made by applying carbon nanotube growth catalyst on to a surface of a wafer substrate to create a dispersed monolayer of catalyst. The substrate is subjected to a chemical vapor deposition of a carbon-containing gas to grow a non-woven fabric of carbon nanotubes in contact and covering the surface of the wafer and in which the fabric is substantially uniform density.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of and claims priority under 35U.S.C. §120 to U.S. patent application Ser. No. 10/341,005, filed Jan.13, 2003, entitled “Method of Making Carbon Nanotube Films, Layers,Fabrics, Ribbons, Elements and Articles” which is a continuation-in-partof and claims priority under 35 U.S.C. §120 to U.S. Pat. No. 6,919,592,filed Jul. 25, 2001, entitled “Electromechanical Memory Array UsingNanotube Ribbons and Method for Making Same” which is acontinuation-in-part of and claims priority under 35 U.S.C. §120 to U.S.Pat. No. 6,706,402, filed Apr. 23, 2002, entitled “Nanotube Films andArticles.”

This application is related to the following applications, all of whichare assigned to the assignee of this application:

Methods of Using Thin Metal Layers to Make Carbon Nanotube Films,Layers, Fabrics, Ribbons, Elements and Articles (U.S. Pat. No.7,560,136), filed on Jan. 13, 2003;

Methods of Using Pre-formed Nanotubes to Make Carbon Nanotube Films,Layers, Fabrics, Ribbons, Elements and Articles (U.S. Pat. No.7,335,395), filed on Jan. 13, 2003; and

Carbon Nanotube Films, Layers, Fabrics, Ribbons, Elements and Articles(U.S. patent application Ser. No. 10/341,130), filed on Jan. 13, 2003.

BACKGROUND

1. Technical Field

The present invention relates generally to nanotube films, layers, andfabrics and methods of making same and, more specifically to carbonnanotube films, layers, and fabrics and methods of making same so thatthey form or may be made to form patterned ribbons, elements andarticles of various shapes and characteristics.

2. Discussion of Related Art

Wire crossbar memory (MWCM) has been proposed. (See U.S. Pat. Nos.6,128,214; 6,159,620; and 6,198,655.) These memory proposals envisionmolecules as bi-stable switches. Two wires (either a metal orsemiconducting type) have a layer of molecules or molecule compoundssandwiched in between. Chemical assembly and electrochemical oxidationor reduction are used to generate an “on” or “off” state. This form ofmemory requires highly specialized wire junctions and may not retainnon-volatility owing to the inherent instability found in redoxprocesses.

More recently, memory devices have been proposed which use nanoscopicwires, such as single-walled carbon nanotubes, to form crossbarjunctions to serve as memory cells. (See WO 01/03208, NanoscopicWire-Based Devices, Arrays, and Methods of Their Manufacture; and ThomasRueckes et al., “Carbon Nanotube-Based Nonvolatile Random Access Memoryfor Molecular Computing,” Science, vol. 289, pp. 94-97, 7 Jul. 2000.)Hereinafter these devices are called nanotube wire crossbar memories(NTWCMs). Under these proposals, individual single-walled nanotube wiressuspended over other wires define memory cells. Electrical signals arewritten to one or both wires to cause them to physically attract orrepel relative to one another. Each physical state (i.e., attracted orrepelled wires) corresponds to an electrical state. Repelled wires arean open circuit junction. Attracted wires are a closed state forming arectified junction. When electrical power is removed from the junction,the wires retain their physical (and thus electrical) state therebyforming a non-volatile memory cell.

The NTWCM proposals rely on directed growth or chemical self-assemblytechniques to grow the individual nanotubes needed for the memory cells.These techniques are now believed to be difficult to employ atcommercial scales using modern technology. Moreover, they may containinherent limitations such as the length of the nanotubes that may begrown reliably using these techniques, and it may difficult to controlthe statistical variance of geometries of nanotube wires so grown.Improved memory cell designs are thus desired.

The reliable fabrication of electrically conductive, ultra-thin metalliclayers and electrodes in the sub-10 nm regime is problematic. (See,e.g., S. Wolf, Silicon Processing for the VLSI era; Volume 2-ProcessIntegration, Lattice Press, Sunset Beach, 1990.) Metal films in thissize regime are usually non-continuous and not conductive overmacroscopic distances. Furthermore, these sub-10 nm films are prone tothermal damage by electrical current, making them unsuitable forapplications such as electrical interconnects in semiconductor devices.Thermal damage of thin metal interconnects caused by their low heatconductivities is one of the main factors inhibiting dramaticminiaturization and performance improvements of highly integratedsemiconductor devices.

Conventional interconnect technologies have a tendency to suffer fromthermal damage and metal diffusion eroding the performance of thesemiconductor devices especially from degradation of the electricalproperties. These effects become even more pronounced with sizereduction in current generation 0.18 um and 0.13 um structures, e.g. bymetal diffusion through ultra-thin gate oxide layers.

There is therefore a need in the art for conductive elements that mayoperate well in contexts having high current densities or in extremethermal conditions. This includes circuit contexts with very smallfeature sizes but includes other high current density, extreme thermalenvironment contexts as well. There is also a need for conductiveelements that will be less likely to diffuse undesirable amounts ofcontaminants into other circuit elements.

SUMMARY

The invention provides new and improved methods of making carbonnanotube films, layers, fabrics, ribbons, elements and articles.

According to one aspect of the invention, carbon nanotube growthcatalyst is applied on to a surface of a substrate. The substrate issubjected to a chemical vapor deposition of a carbon-containing gas togrow a non-woven fabric of carbon nanotubes. Portions of the non-wovenfabric are selectively removed according to a defined pattern to createthe article.

According to another aspect of the invention, a non-woven fabric ofcarbon nanotubes may be made by applying carbon nanotube growth catalyston to a surface of a wafer substrate to create a dispersed monolayer ofcatalyst. The substrate is subjected to a chemical vapor deposition of acarbon-containing gas to grow a non-woven fabric of carbon nanotubes ofnanotubes in contact and covering the surface of the wafer and in whichthe fabric is of substantial uniform thickness.

According to another aspect of the invention, applying the carbonnanotube growth catalyst includes applying metallic nanoparticles.

According to another aspect of the invention, applying the carbonnanotube growth catalyst includes applying metal oxide nanoparticles.

According to another aspect of the invention, the surface of thesubstrate is derivitized to promote adhesion of the carbon nanotubegrowth catalyst.

According to another aspect of the invention, applying the carbonnanotube growth catalyst includes applying a ferritin solution in whichthe ferritin encapsulates metal, and wherein the act of applyingfollowed by oxidizing the ferritin to remove the organic shelltherefrom.

According to another aspect of the invention, applying carbon nanotubegrowth catalyst creates a substantial monolayer of nanoparticles on thesurface of the substrate.

According to another aspect of the invention, applying the carbonnanotube growth catalyst includes applying a metal ligand-catalystprecursor, and wherein the surface is functionalized to promote bindingof the ligand.

According to another aspect of the invention, the metal ligand-catalystprecursor has a formula ML, in which M is metal from a group includingat least iron, cobalt, or nickel, and in which L is an organic ligandhaving a general formula C_(x)H_(y)(COOH).

According to another aspect of the invention, applying the carbonnanotube growth catalyst includes applying a solution of iron oxidenanoparticles on the surface of the substrate.

According to another aspect of the invention, applying the carbonnanotube growth catalyst includes applying a suspension of liquidprecursor to a metal catalyst on the surface of the substrate.

According to another aspect of the invention the carbon-containing gasis methane or ethylene.

According to another aspect of the invention, the chemical vapordeposition is at about 850° C. for about ten minutes and methane isapplied at about a 500 sccm flow or the chemical vapor deposition is atabout 800° C. for about forty minutes and ethylene is applied at about a10 sccm flow.

According to another aspect of the invention, the carbon nanotubes ofthe non-woven fabric include metallic nanotubes and semiconductingnanotubes and the relative composition of metallic and semiconductingnanotubes in the fabric is controlled.

According to another aspect of the invention, the carbon nanotubes ofthe non-woven fabric include metallic nanotubes and semiconductingnanotubes, and semiconducting or metallic nanotubes may be selectivelyremoved therefrom.

BRIEF DESCRIPTION OF THE DRAWINGS

In the Drawing,

FIG. 1A shows a structure, according to certain embodiments of theinvention, having a thin layer of metal catalyst that may be used in anexemplary method of growing nanofabric.

FIGS. 1B.1-1B.2 illustrate exemplary methods of growing nanotube fabricby CVD using the structure of FIG. 1A.

FIGS. 1C-1Z are micrographs of nanofabrics grown with exemplaryprocesses according to certain embodiments of the invention.

FIG. 2 is a cross-sectional view of an exemplary structure used topractice certain embodiments of the invention.

FIG. 3A shows a structure, according to certain embodiments of theinvention, having a distribution of nanoparticles that may be used in anexemplary method of growing nanofabric.

FIG. 3B-C illustrate exemplary methods of growing nanotube fabric by CVDusing the structure of FIG. 3A.

FIGS. 3D-3F are micrographs of nanofabrics grown with exemplaryprocesses according to certain embodiments of the invention.

FIG. 3G-H illustrate exemplary methods of growing nanotube fabric by CVDusing the structure of FIG. 3A.

FIG. 4A shows a structure, according to certain embodiments of theinvention, having a thin layer of metal catalyst and having adistribution of nanoparticles that may be used in an exemplary method ofgrowing nanofabric.

FIGS. 4B-D illustrate exemplary methods of growing nanotube fabric byCVD using the structure of FIG. 4A.

FIG. 5A shows a structure, according to certain embodiments of theinvention, in which a nanofabric is formed over a substrate.

FIG. 5B illustrates an exemplary method of forming nanotube fabric byspin-coating preformed nanotubes in suspension.

FIGS. 5C-5H are micrographs of nanofabrics formed with exemplaryprocesses according to certain embodiments of the invention.

FIGS. 5I-J illustrate exemplary methods of forming nanotube fabric byspin-coating preformed nanotubes in suspension.

FIG. 6 are cross-sectional views of exemplary structures according tocertain embodiments of the invention.

FIG. 7 shows cross-sectional views of exemplary structures according tocertain embodiments of the invention.

FIG. 8A shows cross-sectional views of exemplary structures according tocertain embodiments of the invention.

FIGS. 8B-D are micrographs of nanofabrics patterned according to certainembodiments of the invention.

DETAILED DESCRIPTION

Preferred embodiments of the invention provide nanotube films, layers,or non-woven fabrics and methods of making same so that they form, ormay be made to form, various useful patterned components, elements orarticles. (Hereinafter “films,” “layers,” or “non-woven fabrics” arereferred to as “fabrics” or “nanofabrics”.) The components created fromthe nanofabrics retain desirable physical properties of the nanotubesand/or the nanofabrics from which they are formed. In addition,preferred embodiments allow modern manufacturing techniques (e.g., thoseused in semiconductor manufacture) to be readily employed to utilize thenanofabric articles and devices.

For example, the nanofabrics may be patterned into ribbons, which can beused to create non-volatile electromechanical memory cells. As explainedin U.S. patent application Ser. Nos. 09/915,093 and 10/033,323(incorporated by reference in their entireties), the ribbons may be usedas a component of a non-volatile electromechanical memory cell. Thedeflected, physical state of the ribbon may be made to represent acorresponding information state. The deflected, physical state hasnon-volatile properties, meaning the ribbon retains its physical (andtherefore informational) state even if power to the memory cell isremoved. The nanofabric may also be formed into conductive traces orpads. As explained in U.S. patent application Ser. Nos. 10/128,118 and10/175,586 (incorporated by reference in their entireties), the tracehas advantageous electrical and thermal conductivity, allowing it to beused for extremely small feature sizes, or to be utilized as atransistor component, such as a gate or base of a transistor formingsuperior metal to semiconductor contacts. The nanofabrics may also beformed or patterned into shorter segments such as ribbons or patches.The shorter segments or patches allow facile interconnection of theirnanotubes to vias, interconnects, traces or other structures useful inelectronic devices. They may also be used to create new forms ofelectromechanical memory cells, for example, non-crossbar, embeddedcells. The articles so formed help enable the generation ofnanoelectronic devices and may also be used to assist in increasing theefficiency and performance of current electronic devices using a hybridapproach (e.g., using nanoribbon memory cells in conjunction withsemiconductor addressing and processing circuitry).

Preferred nanofabrics have a plurality of nanotubes in contact so as toform a non-woven fabric. Gaps in the fabric, i.e., between nanotubeseither laterally or vertically, may exist. The fabric preferably has asufficient amount of nanotubes in contact so that at least oneelectrically conductive, semi-conductive or mixed conductive andsemi-conductive pathway exists from a given point within a ribbon orarticle to another point within the ribbon or article (even afterpatterning of the nanofabric).

Though certain embodiments prefer single-walled nanotubes in thenanofabrics, multi-walled nanotubes may also be used. In addition,certain embodiments prefer nanofabrics that are primarily a monolayerwith sporadic bilayers and trilayers, but other embodiments benefit fromthicker fabrics with multiple layers.

To create a nanofabric, the technique chosen must result in a sufficientquantity of nanotubes in contact with other nanotubes which therebymatte as a result of the nanotubes' adhesion characteristics. Certainembodiments (e.g., memory cells) benefit when the nanofabric is verythin (e.g., less than 2 nm); for example, when the nanofabric isprimarily a monolayer of nanotubes with sporadic overlapping (sometimesfabric will have portions that are bilayers or trilayers), or amultilayer fabric with relatively small diameter nanotubes. Moreover,many of these embodiments benefit when the nanotubes are single-wallednanotubes (SWNTs). Other embodiments (e.g., conductive traces) maybenefit from thicker fabrics or multi-walled nanotubes (MWNTs).

The nanotubes have a resistance per square between 1-1000 kΩ/□ (a lowerresistance per square value is generally preferred) but can be tuned tohave a resistance per square between 1 kΩ/□-10 MΩ/□ which is dependentupon the quality of nanotubes used and their electrical and mechanicalcharacteristics. The porosity of the fabric can be tuned as well togenerate low density fabrics with high porosity and high density fabricswith low porosity. The average length of a nanotube ranges between50-1000 nm and 1-100 μm including single-walled nanotubes, multi-wallednanotubes or a mixture of both and can be controlled as is necessary fora particular application such as memory, switches, relays, chemicalsensors, biosensors and resonators.

Certain preferred methods of constructing the nanofabrics involvegrowing nanotubes using chemical vapor deposition (CVD) processes inconjunction with various catalysts. Other preferred methods generatefilms using spin-coating techniques with preformed nanotubes. Thefabrics may be patterned after being formed or they may be grown orformed in a predetermined pattern, e.g., by using patterned catalystmetal layers, nanoparticles or a combination thereof.

Growing Nanofabrics Introduction

Carbon nanotubes can be grown on substrates whose surfaces containcertain metallic or oxide layers. The metallic or metal oxide layersallow metal-containing nanoparticles to be applied onto the substratesurface. Exemplary nanoparticles include metals, such as iron, cobalt,nickel, tungsten, molybdenum, rhenium and other transition metals, ormetal oxides. The metals or metal oxides in these methods act as growthcatalyst for carbon nanotubes.

The literature has documented research results regarding the growth ofsingle-walled nanotubes (SWNTs) from prefabricated nanoparticles (seeKong, J., et al., Chemical Physics Letters, 292, 567, 1998; Li, Y., etal., Journal of Physical Chemistry B, 105, 11424, 2001; Dai, H., et al.,Journal of Physical Chemistry B, 103, 11246, 1999; Colomer, J.-F., etal., Chemical Physics Letters, 345, 11, 2001; and Li, Y. and Liu, J.,Chem. Mater., 13. 1008, 2001), catalyst solutions, e.g., “liquidcatalysts” (see Cassell, A., et al., Journal of Physical Chemistry B,103, 6484, 1999 and Cassell, A., et al., Journal Am. Chem. Soc., 121,7975, 1999), and layered catalytic deposition (Lee Cassell, A., et al.,Journal of Physical Chemistry B, 103, 6484, 1999). Metal oxides ofvarious diameters may be used depending upon whether growth ofsingle-walled nanotubes (SWNTs) or multi-walled nanotubes is desired.(See e.g. Y. Li, W. Kim et al., Growth of Single-Walled Carbon NanotubesFrom Discrete Catalytic Nanoparticles of Various Sizes, Journal ofPhysical Chem. B, 105, 11424, 22 Nov. 2001.) Bi-metallic catalystnanoparticles (iron-molybdenum) have also been fabricated to assist inthe production of carbon nanotubes (see Li, Y. and Liu, J., Chem.Mater., 13. 1008, 2001). These nanoparticles are usually dispersedrandomly on a substrate or other support to produce nanotube growth.Typical liquid catalysts contain a mixture of chlorides or nitrates thathave iron, cobalt, nickel, or molybdenum. These liquid catalysts aregenerated by soaking a pre-patterned ‘stamp’ onto a substrate. Afterstamping, the catalyst is calcinated or oxidized to burn off all thechlorides, nitrides, and other species leaving a random distribution ofmetal nanoparticles within a broad size regime. Yet another method ofproducing SWNTs involves the deposition of metal layers (see Delzeit,L., et al., Chemical Physics Letters, 348, 368, 2001). The metal layersmay include a porous under-layer such as aluminum or iridium, acatalytic layer (iron, cobalt, nickel), and a co-catalyst layer,typically molybdenum. The catalyst nanoparticles required for nanotubeformation are produced during the CVD process.

The inventors have discovered that the above techniques may be extendedto create nanofabrics, which have important characteristics that may becontrolled in the creation process. In addition, they have discoverednew techniques to create nanofabrics. The fabrics can be assembled orgrown (e.g., over an entire wafer surface) and then fabric may beselectively removed, e.g., by using lithographic patterning. In someembodiments, the fabric may be formed in a pattern; i.e., nanotubefabric will grow in places where desired and none need be removedsubsequent to growth.

To grow nanofabrics, the metallic nanoparticles may be applied to thesubstrate surface in a variety of ways, including spin coating,application via aerosol, or by dipping the substrate into a solutionthat includes such nanoparticles. The metallic nanoparticles used ascatalyst may also be applied to the substrate surface by deposition of agas-phase metallic precursor such as any metallocene includingferrocene, molybdocene, cobaltocene and many other derivatives known inthe literature to vaporize at relatively low temperatures, e.g. 25-600°C. (i.e., a low temperature relative to the temperatures at which carbonnanotube growth would occur using that metal as catalyst).

Once a catalyst has been applied to the surface, an appropriatefeedstock gas is supplied to the substrate's environment using a CVDprocess and nanotubes are allowed to grow. Typical growth times rangefrom under 1 minute to 60 minutes. A typical growth phase can becompleted in less than ten minutes. Examples of appropriate feedstockgasses include, but are not limited to CO, CH₄, C₂H₄ and other carbonsources. The feedstock gas should be used at proper flow rates and atproper concentrations with inert gasses such as argon or nitrogen.Typical temperature regimes are about 600-1000° C.

Some factors influencing nanotube growth include catalyst composition,catalyst diameter, catalytic growth efficiency, temperature, CVD runtime and choice of reagents including catalysts and feedstock gasses aswell as reductants and inert carrier gasses, flow rates, ratios ofgasses and mixtures and substrate type and composition.

The films generated by this method are typically characterized in bulkby resistance in ohms per square (Ω/□) measurements that range from 1 to1000 kΩ/□ or in some circumstances from 1 to 20 MΩ/□. This measurementcan be used to describe the quality and density of the tubes in bulkgrowth where lower resistance per square indicates a denser fabric and arelatively high concentration of metallic nanotubes.

Thin Catalyst Layers for Growth of Nanotubes

One preferred method of growing nanofabrics uses CVD techniques withsubstrates having a thin layer of metal catalyst on the substratesurface. The thin layers allow the catalyst to be easily removed insubsequent processing steps. Thicker catalyst layers may require moredifficult processing steps.

FIG. 1A shows a cross-sectional view of an exemplary structure 10 havinga substrate 12 and a thin metal catalyst layer 14 (shown here as onelayer, though more than one layer may be employed). This figure is notto scale; the metal catalyst layer of typical embodiments is only about1-2 nm thick.

An exemplary, non-limiting substrate 12 is made of silicon and has anupper layer of SiO₂ (not shown). The SiO₂ insulates the conductivenanotubes (once formed) from the underlying bulk silicon of substrate12. Moreover, the upper layer of the substrate 12 may already haveformed therein various elements that may be used together with theto-be-formed nanofabric articles to form circuits and the like, or thearticles may be used as conductive connections between circuits formedon the substrate.

The metals that can be used as primary catalyst metals of layer 14 canbe selected from a non-exclusive group known to produce SWNTs, such asiron, nickel, cobalt, and molybdenum. Metal layer 14 can also includemetals that act in conjunction with primary catalysts as co-catalysts,such metals include, but are not limited to, aluminum, molybdenum,cobalt, or other co-catalyst metals. If multi-walled nanotubes (MWNTs)are desired, these and additional transition metals may be used in layer14, such as yttrium, lanthanides and actinides.

The growth of nanotubes from deposited thin metal layers 14 typicallyinvolves the deposition by any physical vapor deposition technique of analuminum layer, an iron layer, and/or a molybdenum layer, onto asubstrate 12. (The aluminum layer generates a porous reactive supportthat aids in generation of carbon species which feed into the ironcatalyst where growth of the nanotubes actually takes place. Themolybdenum layer also serves as a site to reduce the carbon to areactive form. The iron by itself can accomplish this reduction even butin some cases the rate is increased if the Mo and Al are present aswell.) The thin metal layers 14 such as aluminum and molybdenum assistin the formation of SWNTs during CVD (when these three metals are usedin concert, iron is the primary growth catalyst). These layers areextremely thin (e.g., 1-2 nm) and will diffuse or vaporize during CVDgrowth. Some of the particles created from such vaporization may beencapsulated by the eventually-grown nanotubes. (As the nanotubes aregrowing, the thin layers will diffuse. When layers are heated, they havea tendency to generate particles. Some of these particles will containiron which will then be the site of the direct growth of carbonnanotubes. If in some instances the catalyst is very small, then thecatalyst particle will be carried along as the nanotube grows. In othercases the catalyst particle will be larger and the nanotube will growout from this end leaving the catalyst particle in place. Either way, ifone looks at a transmission electron micrograph of a nanotube, one willalmost always find at one end a nanoparticle, which acted as acatalyst.)

FIG. 1B.1 illustrates a way of forming nanofabrics utilizing a substratewith thin metal catalyst layer(s). First, an intermediate structure 10is provided 110. The structure, as outlined above, includes a substrate12 and a metal catalyst layer 14. A furnace is heated 120 to about 500°C. The structure 10 is placed 130 into the furnace. If desired, themetal layer 12 may be oxidized 140 in air. The oxidation can take placeat 500° C. for 30 minutes. Oxidizing may be desired because it generatesnanoparticles on the surface when metal atoms migrate and rearrangethemselves. The temperature of the substrate 10 is ramped up to the CVDtemperature and a flow of feedstock and inert gasses is provided 150.For example, hydrogen gas is mixed with an inert gas that has properheat diffusion properties (typically argon or nitrogen). In someembodiments, the ratio of the gasses can be 1:5 hydrogen to inert gas(the ratio, however, should depend on the flow rate and types of gasintroduced into the system upon reaching CVD temperature). For example,methane at a flow rate of 100-750 standard cubic centimeters per minute(sccm), or ethylene gas at 1.0-5.0 sccm may be used. The CVD run isperformed 160 for some time typically between 1-10 minutes. (A CVDprocess or chemical vapor deposition involves in this case a carrier gas(argon), a reductant (hydrogen) and a carbon feedstock (methane,ethylene in combination or alone, or other gas)). The furnace is rampeddown 170 to less than 200° C. in a flow of inert gas or gasses that havelow or no reactivity with the carbon sources, such as argon or nitrogen.Depending on properties desired in the resulting nanotube fabric, thegas used could be air or oxygen at a lower temperature; such use wouldprovide a final annealing 180 for nanotube adhesion and/or removal ofamorphous carbon. As a result of the above, a nanofabric is created oversubstrate 12 and the thin metal layer 14 is substantially or totallyvaporized.

The surface of the substrate 12 may have a defined pattern (e.g., agrating) on its surface. For example, the surface may have alternatingregions of metal or semiconductor and insulator. The metal orsemiconducting embedded materials may be partially or totally capped offby a sacrificial layer which can be removed later to provide a suspendednanotube nanoribbon structure. See U.S. patent application Ser. Nos.09/915,093 and 10/033,323.

A defined thin metal layer pattern will determine the origination ofnanotube growth. (That is, nanotube growth will originate from thecatalyst regions rather than the interstitial regions which do not havecatalyst. This characteristic may be exploited; i.e., depending on theultimate use of the nanoribbons or nanofabric articles, a specificsurface pattern may be desired (for example in a memory device).Moreover, the thin metal layer catalyst may be patterned to create apatterned growth of nanofabric. If the catalyst patterns aresufficiently far away from each other they may not require subsequentpatterning.

FIG. 2, for example, is a cross-sectional view of an exemplary structure15 having a grating configuration. Surface metal regions 17 areseparated from one another by insulating regions 19. The material ofmetal regions 17 may be selected from appropriate carbon nanotube growthcatalysts, and the insulating regions 19 may be made from material thatdoes not readily initiate carbon nanotube growth and genesis, such assilica. The separate metal catalyst layer regions 17 provide a regionwhere nanotube growth originates.

The density of the nanotube ribbon may be controlled by altering suchvariables as catalyst composition and concentration, growth environment,including but not limited to growth time (e.g., less CVD run time yieldsless dense nanofabric), temperature, gas composition and concentration.Provided below are several exemplary ways of growing nanofabrics usingthe above principles.

Example 1

Thin metal layers of aluminum, iron, and molybdenum (15 nm, 1 nm, and 2nm, respectively) are sequentially deposited on a substrate. Thesubstrate is placed in a tube furnace in which the temperature is rampedto 500° C. and held for thirty minutes, in an ambience of air. Thetemperature is then ramped to a CVD temperature of 850° C. in a flow ofargon gas and hydrogen gas, at 100:400 sccm Ar:H₂ Upon reaching the CVDtemperature, methane gas at a flow rate of 500 sccm is introduced intothe furnace for a 1 minute growth time. Completing the CVD, the furnaceis ramped down to below 200° C. in an argon atmosphere. FIG. 1C is amicrograph of a fabric made from this procedure.

Example 2

All parameters of example 1 are duplicated except in place of methane,ethylene is used at a flow rate of 5.0 sccm for 10 minutes, the CVDtemperature is 800° C. The same types of metal layers are employed;however, the thicknesses of the metal layers used are 5 nm aluminum, 1nm iron, and 2 nm molybdenum. FIG. 1D is a micrograph of the nanotubegrowth resulting from such use of ethylene.

Examples 3-6

Examples 3-6 show that the rate of methane gas flow affects theproduction of nanotube fabrics in typical CVD methods. From themicrographs one can see how the change in gas flow from 725 to 500 to250 sccm affects the amount of growth. These examples show that theporosity and type of nanotubes grown may be controlled by changingspecific parameters in the growth process. The growth of nanotubes issustained over this range and can be finely controlled to generateprimarily multilayer fabrics (750 sccm) to primarily monolayer fabrics(250 sccm). Reduction in gas flow to even lower levels is possible toassure primarily monolayer fabrics. An increase of the concentrationwould allow growth of fabrics with multilayers. Other parameters such asgrowth time and temperature can be controlled in concert with feedstockgas flow to provide more control over the fabric's characteristics.

Example 3

Methane is flowed at 725 sccm and the argon and hydrogen gas flow arekept constant at 100 sccm and 400 sccm, respectively. CVD is performedas above with the following parameters: the CVD is performed at 850° C.for 1 minute with the following metal layers: 15 nm aluminum, 1 nm ironand 2 nm molybdenum. FIG. 1E is a micrograph of the film which resultedfrom this procedure.

Example 4

All parameters are kept the same as example 3 except methane gas flow is500 sccm. FIG. 1F is a micrograph of the film which resulted from thisprocedure.

Example 5

All parameters are kept the same as example 3 except methane gas flow is250 sccm. FIG. 1G is a micrograph of the film which resulted from thisprocedure.

Example 6

All parameters are kept the same as example 3 except methane gas flow is100 sccm. FIG. 1H is a micrograph of the film which resulted from thisprocedure.

Examples 7-9

Examples 7-9 mirror examples 3-6 in that the flow rates of ethylene gasused are decreased in sequential CVD processes, while keeping all othervariables constant. As above, all of these examples show fine controlmay be achieved over the growth density, nanotube porosity, nanotubelength and the resistance per square values. (Resistance per square isused to assess in general the porosity of the nanotubes and/or theiroverall conductive quality.) Figures for examples 7-9, respectively,show fabrics corresponding to decreasing the gas flow. As flowdecreases, the fabric density decreases and resistance increases.

Example 7

The argon flow and hydrogen flow are kept constant at 100 sccm and 400sccm, respectively. Ethylene gas is flowed at 5.0 sccm. Metal layers areas follow: 5.0 nm aluminum, 1.0 nm iron and 2.0 nm molybdenum, the CVDtemperature is 800° C., and is run for 10 minutes. FIG. 1I is amicrograph of the film, which resulted from this procedure.

Example 8

All parameters are kept the same as example 7 except ethylene gas flowis 2.5 sccm. FIG. 1J is a micrograph of the film which resulted fromthis procedure.

Example 9

All parameters are kept the same as example 7 except ethylene gas flowis 1.0 sccm. FIG. 1K is a micrograph of the film which resulted fromthis procedure.

Examples 10-12

Examples 10-12 show the effects of reducing CVD temperatures whilekeeping all other parameters constant. The CVD methods are otherwisemuch the same as in example 1. These examples also show that finecontrol may be achieved in porosity, thickness and length of nanofabricsand nanotubes. Figures for examples 10-12, respectively, show fabricscorresponding to decreasing CVD temperatures. As the temperaturedecreases, the fabric density decreases, and the resistance increases.

Example 10

CVD is performed on a substrate of silicon coated with 15 nm aluminum, 1nm iron and 2 nm molybdenum, using a 725 sccm flow of methane gas at900° C. for ten minutes in Ar/H flow as above. FIG. 1L is a micrographof the film which resulted from this procedure.

Example 11

All parameters are kept the same as in example 10, except the CVDtemperature is decreased to 850° C. FIG. 1M is a micrograph of the filmwhich resulted from this procedure.

Example 12

All parameters are kept the same as in example 10, except the CVDtemperature is decreased to 800° C. FIG. 1N is a micrograph of the filmwhich resulted from this procedure.

Examples 13-16

Figures for examples 13-16, respectively, show fabrics corresponding todecreasing CVD run time. As the run time decreases, the fabric densitydecreases, and the resistance increases.

Example 13

CVD is run for 10 minutes on a substrate of silicon coated with 15 nmaluminum, 1 nm iron, and 2 nm molybdenum at 850° C. in a 725 sccm flowof methane gas and 100:400 sccm Ar:H₂ as above. FIG. 1O is a micrographof the film which resulted from this procedure.

Example 14

All parameters are kept the same as example 13, except the CVD run timeis decreased to five minutes. FIG. 1P is a micrograph of the film whichresulted from this procedure.

Example 15

All parameters are kept the same as in example 13, except the CVD runtime is decreased to two minutes. FIG. 1Q is a micrograph of the filmwhich resulted from this procedure.

Example 16

All parameters are kept the same as in example 13, except the CVD runtime is decreased to one minute. FIG. 1R is a micrograph of the filmwhich resulted from this procedure.

Examples 17-20

Examples 17-20 show the effect that varying the thicknesses of thealuminum metal layer has on the resulting films. As above, all of theseexamples show fine control may be achieved over the growth density,nanotube porosity, nanotube length and the resistance per square values.Figures for examples 17-20, respectively, show fabrics corresponding todecreasing thickness of the metal layer catalyst. As the thicknessdecreases, the fabric density decreases, and the resistance increases.

Example 17

CVD is performed on a substrate of silicon coated with 25 nm aluminum, 1nm iron and 2 nm molybdenum, using a 725 sccm flow of methane gas andthe argon and hydrogen gas flow are kept constant at 100 sccm and 400sccm, respectively, at 850° C. for ten minutes. FIG. 1S is a micrographof the film which resulted from this procedure.

Example 18

All parameters are kept the same as in example 17, except the thicknessof the aluminum layer is decreased to 15 nm. FIG. 1T is a micrograph ofthe film which resulted from this procedure.

Example 19

All parameters are kept the same as in example 17, except the thicknessof the aluminum layer is decreased to 5 nm. FIG. 1U is a micrograph ofthe film which resulted from this procedure.

Example 20

All parameters are kept the same as in example 17, except the thicknessof the aluminum layer is decreased to 0 nm (no aluminum is deposited inthis example). FIG. 1V is a micrograph of the film which resulted fromthis procedure.

Examples 21-22

Examples 21-22 show the results of altering thin metal layer thicknessand using silicon dioxide as substrate. Altering the metal layerthickness allows tuning of the porosity and specifically the type ofnanotubes. Thicker layers are more conducive to growing MWNTs whilethinner layers grow better SWNTs and leave less residual metal becausethey are vaporized at the high temperatures of nanotube growth. Figuresfor examples 21-22, respectively, show fabrics corresponding todecreasing thickness of the metal layer catalyst. As the thicknessdecreases, the fabric density decreases, and the resistance increases.

Example 21

CVD is performed on a silicon dioxide substrate coated with thin metallayers; 2.0 nm aluminum, 0.5 nm iron and 1.0 nm molybdenum at 850° C. ina 500 sccm flow of methane gas in 100:400 sccm Ar:H₂ for one minute.FIG. 1W is a micrograph of the film which resulted from this procedure.

Example 22

All parameters are kept the same as example 21, except thin metal layersof the following thicknesses; 1.0 nm aluminum, 0.5 nm iron and 1.0 nmmolybdenum were used. FIG. 1X is a micrograph of the film which resultedfrom this procedure.

Examples 23-24

Examples 23 and 24 show the films that are grown by CVD on silicon andsilicon dioxide substrates. These examples illustrate control overporosity even on different substrates. Here we have an example of asemiconducting substrate and an insulating substrate. Growth isachievable on a variety of substrate layers allowing ready integrationinto typical semiconductor process flows and ease of manufacture.Figures for example 23 and 24 show that the fabric density changes withthe type of substrate, and thus resistance changes.

Example 23

CVD is performed on a silicon substrate coated with thin metal layers;15 nm aluminum, 1.0 nm iron and 2.0 nm molybdenum at 850° C. in a 500sccm flow of methane gas for two minutes. FIG. 1Y is a micrograph of thefilm which resulted from this procedure.

Example 24

All parameters are kept the same as example 23, except silicon dioxideis used as substrate. FIG. 1Z is a micrograph of the film which resultedfrom this procedure.

Growing Nanofabrics with Nanoparticles

Another preferred method of growing nanofabrics uses metallic or metaloxide nanoparticles (e.g., iron oxide) as carbon nanotube growthcatalyst. Metallic or metal-oxide nanoparticles have a narrow range ofdiameters. This narrow range can lead to more effective control over thediameter and type of nanotubes forming the eventual nanofabric. Thesurface of the substrate used can be derivitized to create a morehydrophobic or hydrophilic environment to promote better adhesion of thecatalyst particles. The nature of the substrate allows control over thelevel of dispersion of the nanoparticles to a precision sufficient togenerate monolayer nanotube fabrics.

FIG. 3A shows a cross-sectional view of an exemplary structure 20 usedto grow nanofabrics. A substrate 12 has a distribution 16 of metallic ormetal oxide nanoparticles thereon. (For simplicity, the figure shows thedistribution as a continuous layer, though people skilled in the artwill appreciate that in reality the structure 20 will have adistribution of relatively discrete nanoparticles.) The substratesurface used for generation of carbon nanotubes may be any materialincluding, but not limited to, silicon, thermal oxide, silicon oxide,silicon nitride, tungsten, tungsten/titanium and other typicalinsulators, semiconductors and metallic surfaces commonly used in CMOSand semiconductor fabrication processes the surface may have electroniccomponents and patterns already defined therein, as mentioned above, andthe substrate may be functionalized or non-functionalized.

FIG. 3B illustrates a way of growing a nanofabric using a substratecoated with nanoparticles 16. A mixture of ferritin and water iscreated. For example, ferritin dissolved in deionized (DI) water at atypical concentration (1-1000 μM) (SIGMA catalog) is provided. Theferritin contains naturally encapsulated iron in an organic layer orshell, and can be processed so that the encapsulated iron may be used insubsequent nanotube generation. This shell is oxidized using air oroxygen oxidation or plasma ashing, which causes its removal leaving onlyan iron oxide nanoparticle. During CVD growth of nanotubes the ironoxide nanoparticles are reduced to leave metallic iron nanoparticleswhich catalyze the growth of nanotubes. The purpose of using ferritin orany appropriate nanoparticles is to cause the nanoparticles to bedispersed on the surface in an even fashion (monodisperse). Ferritinparticles have a very narrow diameter range as do the nanoparticlesdiscussed below.

The ferritin solution is applied 310 to a surface of substrate 12.Before application the substrate can be derivitized to make it morehydrophilic or hydrophobic in order to promote adhesion of the ferritinto the surface. The substrate is allowed to dry 320 (e.g. approximatelyfive minutes has been found to be sufficient). This leaves a coating offerritin on the surface of the substrate. The protein shells are thenremoved 330 from the ferritin particles. For example, the structure maybe subjected to either an oxidation operation at 400-800° C. for about15 minutes, or it may be subjected to a plasma ashing operation. Theoxidation process removes substantially all of the proteinaceous shellfrom the ferritin, thereby leaving behind a coating 16 of nanoparticlesof iron oxide. The nanoparticles are approximately two to fivenanometers in diameter, or more particularly approximately threenanometers in diameter. (See Li, 46 Journal Physical Chem. above.) Oncecatalyst particles from ferritin are formed, CVD may be performed 340 togrow a nanofabric of nanotubes. The nanofabric may be grown, forexample, over an entire wafer surface as a monolayer of contactingnanotubes. The above embodiment is conducive to growing a conductive(primarily) monolayer fabric with sufficient density to remain suspendedover a switching junction.

Under yet other embodiments, metal ligand-catalyst precursor moleculesare used to deposit metallic nanoparticles on a functionalized substratesurface to thereby help create growth of nanotubes. Typically, theformula of the metal/ligand complex will have a formula such as ML, inwhich M is a metal such as iron, cobalt, or nickel, and L is one or moreorganic ligands having an affinity for the metal. One general formulamay be C_(x)H_(y)(COOH), but other carbon, oxygen, nitrogen and/orsulfur-containing ligands are known and may be used. A metallicnanoparticle ligated to an organic moiety is deposited on afunctionalized substrate surface. The surface is functionalized tooptimize ligand bonding during spin coating, a procedure which mayresult in minimal deposition of untreated nanoparticles. Certainembodiments use a generic method to synthesize metallic nanoparticleswith organic shells which have a very specific size regime for example3-5 nm which can be monodisperse on a substrate.

Certain embodiments use prefabricated iron oxide particles as carbonnanotube growth catalyst. Iron oxide nanoparticles are applied to asubstrate in a concentration sufficient to support the desired densityof nanotube growth. The substrate is then subjected to a CVD operationas described herein. The substrate, optionally, can be dried and/oroxidized prior to beginning the CVD run. For example, iron oxidenanoparticles may be applied to a substrate surface by spin coating. Inone embodiment, iron oxide is suspended in deionized water at a 1:10ratio. The aqueous iron suspension is applied to a substrate surface,and the surface is spun at approximately 1000 rpm to distribute thesuspension. The surface is then spun at 4000 rpm to dry the suspension.More than one application of iron oxide nanoparticles may be performed.The number of applications of iron oxide nanoparticles required willvary depending on the concentration of the suspension used, the desiredresulting surface density of nanoparticles, the physical properties ofthe desired fabric, and the physical properties of the substrate used.

Under yet other embodiments, a liquid catalyst precursor suspension isused. FIG. 3C illustrates a way of growing a nanofabric using liquidmetal catalyst. A liquid metal catalyst is created. For example, adissolved metal catalyst, e.g., iron nitrate (Fe(NO₃)₃, is mixed withmethanol and applied onto a substrate 350. The substrate is oxidized360, e.g., by ashing, thereby leaving a dispersion of iron oxidenanoparticles on the surface of the substrate. The substrate is thensubjected to a CVD operation 370 to grow nanotubes. Provided below areseveral exemplary ways of growing nanofabrics using the aboveprinciples.

Example 25

This is an example of nanoparticles using metal-ligand catalystprecursor molecules. HMDS (hexamethyldisilane) is spun onto a silicondioxide substrate at 4000 rpm for one minute as an adhesion layer. Ironnanoparticles are made by dissolving Fe(NO₃)₃ in solution of a lauricacid in methanol at a ratio of 1:3.3 Fe:lauric acid. The nitratesolution is evacuated to pump off nitric acid, and the solvent. Thedried iron nanoparticles are then added to 10 mL toluene and 10 mLisopropanol to resuspend the nanoparticles in solution. The Fenanoparticle solution is then diluted 1:25 in isopropanol. The ironnanoparticles in a 1:25 iron nanoparticle solution in isopropanol isthen deposited on the wafer by spinning at 1000 rpm for 30 seconds, thenat 4000 rpm for 20 seconds. Two Fe nanoparticle applications aredeposited and spun. The substrate is baked at 100° C. to remove thesolvent, it is then ashed for 30 minutes in O₂ plasma, CVD is performedat 850° C. for ten minutes in a 500 sccm flow of methane and a 100:400sccm flow of Ar:H₂. FIG. 3D is a micrograph of a nanofabric whichresulted from this procedure. The nanoparticles in this embodiment canbe tuned to a particular size by changing the organic ligand (analogousto the protein shell of ferritin) that is bound to the metal.Additionally, nanoparticles of different metal or metal oxide speciesmay be mixed together in a solution and applied for use as catalyst,e.g., 50% Fe and 50% Co, or 33% Fe 33% Co and 33% Al, or any otherappropriate combinations.

Example 26

This is an example of iron nanoparticles in solution which are dispersedonto a silicon dioxide substrate and not spin coated on the surface.After the catalyst is dispersed onto the surface, the substrate isallowed to stand for 5 min., covered, and baked at 100° C. to removesolvent, and it is ashed. CVD is performed at 850° C. for ten minutes ina 500 sccm flow of methane and a 100:400 sccm flow of Ar:H₂. FIG. 3E isa micrograph of a nanofabric which resulted from this procedure.

Example 27

Example 27 demonstrates the growth of carbon nanotubes from a substratewith ferritin on the surface. The process involves the use of ferritinas a catalyst precursor. A 1:10 mixture of ferritin in deionized wateris applied to a silica surface of a wafer. The wafer is dried, leaving adispersed coating of ferritin on the surface of the substrate. Thesubstrate is oxidized to remove all non-iron, organic matter and placedin the oven. The oven is ramped to 700° C. for 10 minutes in Ar:H₂, thenit is ramped to 800° C. for seven minutes in Ar:H₂. CVD is performed at800° C. with a 10 sccm flow of ethylene for 40 minutes in 600:400 sccmAr:H₂. FIG. 3F shows a FESEM micrograph of carbon nanotubes grown usingferritin as catalyst precursor.

Growing Nanofabrics with a Combination of Nanoparticles and Thin MetalLayers

Another preferred method of growing nanofabrics uses nanoparticles inconjunction with thin metal layers on a substrate surface. This methodallows one to easily distribute catalyst particles while takingadvantage of the ease of thin layer deposition and their properties inassisting the process of growing nanotubes. Recall that aluminum andmolybdenum are useful in generating surface carbon precursors that grownanotubes.

FIG. 4A shows a cross-sectional view of an exemplary structure 30 usedto grow nanofabrics. A substrate 12 has a thin layer 14 of metalcatalyst and a distribution 16 of nanoparticles thereover. The substratesurface used for generation of carbon nanotubes may be any materialincluding, but not limited to silicon or thermal oxide, e.g. siliconoxide, alumina. The uppermost layer can be an insulator, semiconductoror metal. Typical substrates which are of interest include silicondioxide (SiO₂), silicon nitride (Si₃N₄), titanium, titanium/tungsten andothers used in standard CMOS and semiconductor processing. The surfacemay have already formed therein various components and structures (e.g.,gratings) of the aforementioned materials. In addition, the surface maybe functionalized or non-functionalized.

FIG. 4B illustrates a way of growing a nanofabric of carbon nanotubes(e.g., to cover a wafer surface) by using nanoparticles in conjunctionwith thin metal layers. First, a substrate 12 is provided and a thinlayer of metal catalyst is provided 410 to at least selected regions ofa wafer or perhaps an entire wafer surface, as described above. Thisforms layer 14 of metal catalyst. Thereafter, a distribution ofnanoparticles 16 is applied 420 to the surface of layer 14. This may bedone using any of the above methods of applying nanoparticles, e.g.,spin coating suspensions of nanoparticles. Catalyst precursors such asferritin, liquid metal catalyst precursor and metal ligand-catalystprecursor molecules may also be used in conjunction with thin metallayers on substrates to grow carbon nanotube fabrics. Depending on howthe nanotubes are applied, the substrate may be dried (optionally) 425.The substrate is oxidized 430. Once so formed, the structure 30 may besubjected to a CVD process 440 to form a nanofabric.

Forming Nanofabrics With Pre-Formed Nanotubes Introduction

One preferred method of forming a nanofabric uses spin coatingtechniques in conjunction with pre-formed nanotubes. Nanotubes should besufficiently free of amorphous carbon if the nanotubes are to be used aselectronic elements. Among other advantages, this technique is moreconducive to semiconductor manufacturing environments than growth ofnanotubes by CVD because it uses a room temperature process that doesnot contribute to the thermal budget of the standard CMOS process flowsor semiconductor manufacturing methods. Additionally, the overall costof this integration of nanotubes is very inexpensive.

FIG. 5A shows an exemplary structure 50 having a wafer substrate 12 anda nanofabric 54 thereover. The nanofabric 54 may be made to cover anentire wafer surface.

An exemplary, non-limiting substrate 12 is like those described above.The substrate may be any material that will accept the deposition ofnanotubes by spin coating, but preferably a material chosen from thegroup consisting of a thermal oxide or nitride, including but notlimited to silicon dioxide, silicon nitride, alumina on silicon, or anycombination of the following on silicon or silicon dioxide: aluminum,molybdenum, iron, titanium, platinum, and aluminum oxide, or any othersubstrate useful in the semiconductor industry.

Spin Coating Nanotubes on Functionalized Substrate Surfaces

FIG. 5B shows a way of making a fabric of nanotubes on a functionalizedcarbon nanotube growth substrate surface 52. The substrate surface 52may be prepared for spin coating by functionalizing the surface.Specifically, functionalization of a wafer/substrate surface involvesderivitizing the surface of the substrate. For example, one couldchemically convert a hydrophilic to hydrophobic state or providefunctional groups such as amines, carboxylic acids, thiols orsulphonates to alter the surface characteristics of the substrate.Functionalization may include the optional primary step 510 of oxidizingor ashing the substrate in oxygen plasma to remove carbon and otherimpurities from the substrate surface and to provide a uniformlyreactive, oxidized surface which is then reacted with a silane. One suchpolymer that may be used is 3-aminopropyltriethoxysilane (APTS). Thesubstrate surface 52 may be derivitized 520 prior to application of ananotube suspension to enhance bonding of the nanotubes. The inventorsforesee that any reactive silane could be used in functionalization ofsuch a surface. In a particular, non-limiting embodiment, the substratesurface 52, whether or not subjected to ashing, is exposed to anapproximately 1 to 50 millimolar solution of APTS in suitable organicsolvent, e.g. hexane, but more preferably 13 to 28 millimolar APTS inhexane, such that approximately a monolayer of APTS is deposited on thesubstrate surface. In order to form such a monolayer of APTS, thesubstrate typically is immersed in an APTS solution for 30 minutes. Oncethe surface 52 is prepared for spin coating, carbon nanotubes aredispersed 530 on the surface, and the surface is subjected to spinningin order to disperse the nanotubes, forming a nanotube fabric (e.g.,fabric 54 of FIG. 5A). The substrate is then (optionally) annealed 540.

Different methods may be employed to apply nanotubes to surfaces to formnanofabrics: to attain desired fabric properties; the selection of onemethod over another depends, in part, on the properties of thepre-formed nanotubes being used. For example, under certain embodimentslaser-ablated SWNTs are used; under other embodiments,commercially-available high pressure carbon monoxide decomposition SWNTsnanotubes are used, such as HiPco™ nanotubes available from RiceUniversity; under still other embodiments, other nanotubes may be used.

Under some embodiments, laser-ablated nanotubes are mixed with a solventat a concentration of about 100-500 μg/mL. Solvents which are quiteuseful for suspension of SWNTs and distribution via spin coating includeisopropanol, methanol, ethanol, 1,2 dichlorobenzene, 1,3dichlorobenzene, 1,4 dichlorobenzene, chlorobenzene,n-methylpyrollidinone, dimethylformamide, dimethylsulfoxide,acetonitrile, hexane, toluene, methylene chloride and chloroform. Whileall of these solvents have the ability to suspend nanotubes, the precisecharacteristics of the film desired and substrate used are important forsolvent selection. If a low boiling solvent is desired hexane would, forexample, be a better selection than DMSO. 1,2 dichlorobenzene is apreferred solvent owing to its excellent suspension properties andcompatibility with industrial semiconductor processes.

Under some embodiments, HiPco™ nanotubes may be used. The HiPco™nanotubes are SWNTs and relatively free from amorphous deposits, fibrousdeposits and other impurities. HiPco™ tubes are mixed intoorthodichlorobenzene at a more dilute concentration than are laserablated nanotubes, typically 10-200 μg/mL.

Under the above embodiments, the preferred concentration depends on thelength of the nanotubes used. Laser ablated nanotubes tend to haveoverall greater lengths than HiPco™ tubes. Regardless of the nanotubesused, the nanotubes in mixture should be adequately dispersed, e.g., bysonication.

Adequately-dispersed nanotubes may be applied 530 onto a substratesurface by spin coating. Such a surface should be relatively free of anyresidue remaining after storage or after any substrate preparation step,e.g. functionalization of the surface. If solvent, e.g. hexane ispresent on the substrate's surface, it may be removed, e.g., by bakingat 100-115° C. for 1 minute. After removal of any storage solvent, thenanotubes are spun onto the substrate surface.

One way of spin coating the nanotubes involves spinning the substrate,for example, at 1000 rpm while depositing the nanotube solution on thesubstrate surface, for about 30 seconds or alternatively they can beapplied before the spinning has begun. The substrate may (i.e.,optionally) then be dried, for example, by spinning at 4000 rpm untildry. Further coats of nanotube suspension may be applied in like manner,until the substrate surface is coated with the desired density ofnanotubes. Ribbon density may be varied based on desired use. Adequatelayers of nanotubes typically have resistance per square measurementsbetween 1-1000 kΩ/□. For particular applications, nanotube layers withresistances per square below 1 kΩ/□ may be preferred, and for yet otheruses, nanotube films with resistance per square measurements of 1-10MΩ/□ may be sufficient. Typically four coatings of the nanotubesuspension are applied to the substrate surface to create a fabric thatwill have a redundancy of electrically conductive pathways. After alayer of nanotubes of desired density, i.e., a monolayer, is spun ontothe substrate, the substrate may be baked 540 once again to remove anyremaining solvent, e.g., at 100-115° C. After four coatings are appliedas described, a fabric resistance per square of ˜100 kΩ is typicallymeasured. The actual resistance per square depends upon the quality ofthe nanotubes used, their compositions, and overall purity.

Spin Coating Nanotubes on Non-Functionalized Substrate Surfaces

A non-functionalized substrate surface may be coated with nanotubes byspin coating. The surface may be oxidized, e.g., by ashing in oxygenplasma, to remove surface impurities, or it may be coated and notoxidized. The nanotubes used may be, but are not limited to,laser-ablated SWNTs or HiPco™ nanotubes.

Adequately dispersed nanotubes may be deposited on a non-functionalizedsubstrate surface by spin coating. Similarly to the above, the substratemay be spun at 1000 rpm for 30 seconds while applying a nanotubesolution to the substrate surface to distribute the nanotubes or thesolution may be applied first and then spun. Further coats of nanotubesuspension may be applied until the substrate surface is coated with thedesired density of nanotubes. The substrate may be dried (optionally)between application steps, e.g., by spinning at 4000 rpm until dry.

Similarly to the above, ribbon density may be varied based on desireduse. Typically, eight coatings of the nanotube suspension are applied tothe non-functionalized substrate surface, when using the precedingparameters, to attain a fabric of electrically conductive nanotubes.After a layer of nanotubes of desired density is spun onto the substratesurface, the substrate can be baked once again to remove any remainingsolvent, e.g. at 100-115° C. Such a method typically results in ananotube layer resistance per square measurement of ˜1-100 kΩ which isdependent both on the number of applications performed and the purityand character of the nanotubes used. Because nanotubes that have beendeposited on a surface may be solvated and removed by subsequentapplications of nanotubes in solvent, it may be desirable to cure thesubstrate and nanotubes before subsequent applications of solvatednanotubes. Such curing may be accomplished through evaporation ordrying. Another way of limiting the subsequent dissolution and removalof already-spun-on tubes (removal by dissolution and from thecentrifugal force overcoming van der Waals attraction between thenanotubes and the substrate surface) is to use a different solvent forsubsequent spin coating steps.

The density of the nanotube ribbon may be controlled by altering suchvariables as including but not limited to functionalization of theunderlying surface, spin coating parameters (length of time and RPM),solvent choice, nanotube type and concentration, diameter and length ofnanotubes, number of applications and substrate type and composition.

Provided below are several exemplary ways of forming nanofabrics usingthe above principles.

Example 28

A wafer substrate is first ashed in oxygen plasma for 15 minutes. Afterashing, the substrate is bathed for 30 minutes in a solution of3-aminopropyltriethoxysilane (APTS), the functionalization agent, andhexane at a ratio of 30-60 μL of APTS to 10 mL of Hexane. During thesurface functionalization step, a nanotube solution is prepared. HiPcO™SWNTs are mixed in a solution comprising 1 mg of nanotubes and 50 ml 1,2dichlorobenzene. The nanotube solution is then sonicated for 1 hour toadequately disperse the nanotubes in the solvent solution. Beforenanotube deposition, the substrate is removed from the hexane bath andis baked at 100-115° C. for 1 minute to remove any solvent residue.After baking, the nanotubes are spun onto the wafer at 1000 rpm for 30seconds to distribute the nanotubes, and then they are spun at 4000 rpmto dry the wafer. Four such SWNT spin coatings are applied to the wafer.After spinning, the wafer is baked again at 100-115° C. to remove anyremaining solvent.

A resistance per square measurement of 1-100 kΩ was measured. FIGS. 5C-Ddisplay FESEM images of different magnifications of HiPco™ SWNTs spunonto a functionalized surface.

Example 29

All parameters are kept the same as in example 28 except 10 mg oflaser-ablated nanotubes are mixed in 100 mL of 1,2 dichlorobenzene andare spun onto a wafer surface. A resistance per square of 100-400 kΩ wasmeasured. FIG. 5E displays a FESEM image of spun-on laser-ablated SWNTswith a functionalized surface. Some particles containing amorphouscarbon impurities are observed also.

Example 30

All parameters are kept constant as in example 29, except the substrateused for spin coating was stepped, i.e., not horizontally planar. FIG.5F displays a micrograph of a nanofabric spun on to the substrateaccording to this method; the micrograph shows that nanotubes conform toa substrate surface via van der Waals attraction. The inventorscontemplate that conformal nanofabrics may be useful in fabrication ofnon-horizontal electromechanical switches, especially verticalelectromechanical switches or also as interconnects, actuators, relays,sensors and other electronic elements.

Example 31

Carbon nanotubes are deposited on a non-functionalized surface asfollows. A wafer surface is ashed for 1 minute. A nanotube solution isdeposited and spun on to the wafer as presented in Example 28, above.Eight applications of nanotube mixture are applied to the wafer surface,producing resistance per square measurements on varying sections of thenanotube fabric ranging from 50 to 100 kΩ. FIG. 5G displays an FESEMimage of SWNTs spun onto a non-functionalized wafer surface withsufficient applications to generate a multilayer nanofabric. FIG. 5Hdisplays an FESEM micrograph of a monolayer fabric spun onto a substratewhich has a prefabricated metal electrode with a width of about 130 nmshown.

Preferred embodiments operate with a range of concentrations forpre-formed nanotubes. For example for laser ablated nanotubes aconcentration of about 0.1-0.5 mg/mL (100-500 ug/mL) is used. Theconcentration is preferably adjusted depending upon the purity andlength of the nanotubes; for example, shorter nanotubes have onespinning regime and longer ones have a different regime.

In addition, preferred embodiments preferably subject the nanotubesolution to sonication. For example, preferred embodiments usesonication times such as 30-120 minutes.

Patterning Nanofabrics

The new and improved methods for creating nanofabrics may be used tocreate articles therefrom. The U.S. patent applications, identified andincorporated above, describe specific (but not limiting) uses of suchfabrics and articles. For example, the various masking and patterningtechniques for selectively removing portions of the fabric are describedin these applications but are not repeated here for the sake of brevity.Moreover, various component architectures are described in theincorporated applications but not repeated here for the sake of brevity.

FIG. 6, for example, is a cross-sectional view of exemplary structuresused in creating patterned nanofabrics. This method creates patches ofcarbon nanotube fabric which can be used as electronic elements. Such apatch of nanotube fabric may be used as an electromechanical switch, oras an electronic interconnect. An intermediate structure 600 isprovided. Structure 600 comprises a nanofabric 620 overlying a substrate610. The substrate 610 could be a simple substrate made of a singlematerial; it could be a substrate which has already undergone someprocessing, e.g., to include vias, plugs or other elements, etc. Thenanofabric 620 may be grown or formed using any of the methods disclosedor incorporated above. The nanofabric may be of SWNTs or multi-wallednanotubes. A layer of resist 630 is applied over the nanofabric 620 toform intermediate structure 640. The resist 630 is then patterned usingany of a variety of techniques, including but not limited to thosedescribed in the incorporated references. For example, the resist may bepatterned to correspond to the desired pattern of nanofabric patches, sothat the resist will cover (and define) the desired patches. Removingselected portions of the resist (e.g., exposed portions) will createintermediate structure 650. The intermediate structure 650 includesexposed nanofabric portions 670 and remaining resist portions 660. Theexposed nanofabric portions 670 may be removed in many ways; forexample, by performing a reactive ion etch procedure, or oxidizing thesubstrate, by plasma ashing, air oxidation or other reaction methods toremove all nanotube fabric except for the desired patches, therebycreating intermediate structure 680. The remaining resist portions 660may then be stripped from intermediate structure 680, yielding structure690 which includes patterned patches 695 of nanofabric.

As explained in the incorporated references, the nanofabric 620 may beformed or grown over defined regions of sacrificial material and overdefined support regions. The sacrificial material may be subsequentlyremoved, yielding suspended articles of nanofabric. See, for example,Electromechanical Memory Array Using Nanotube Ribbons and Method forMaking Same (U.S. patent application Ser. No. 09/915,093) filed Jul. 25,2001, for an architecture which suspends ribbons of nanofabric.

FIG. 7, for example, is a cross-sectional view of exemplary structuresused in creating suspended, patterned nanofabrics. This method createssuspended patches of carbon nanotube fabric, which can be used aselectronic elements. Such a patch of nanotube fabric may be used as anelectromechanical switch, or as an actuator, a relay, a sensor,especially a biosensor or chemical sensor.

An intermediate structure 700 is provided. Structure 700 comprisesdefined regions of sacrificial material 720 overlying a substrate 710(which as outlined above could made of a single material; could be asubstrate which has already undergone some processing, e.g. to includevias, plugs or other elements, etc.). A nanofabric 730 covers thesubstrate surface and the sacrificial material 720. The nanofabric 730may be formed or grown as outlined above and may be multilayer or singlelayer and may have single- or multi-walled nanotubes. A layer of resist740 is applied over the nanofabric 730 to create intermediate structure745. The resist 740 is then patterned (not shown). Removing selectedportions of the resist (e.g., exposed portions) will create intermediatestructure 750. The intermediate structure 750 includes exposednanofabric portions 770 and remaining resist portions 760. The exposednanofabric portions 770 may be removed in many ways; for example, byperforming a reactive ion etch procedure, or oxidizing the substrate, byplasma ashing, air oxidation or other reactive methods to remove allnanotube fabric except for the desired patches, thereby creatingintermediate structure 780. The remaining resist portions 760 may thenbe stripped from intermediate structure 780, yielding structure 790which includes patterned nanofabric patches 795 overlying definedsacrificial material 720. The sacrificial layer 720 is removed byselective etching, leaving substantially intact the suspended patternednanofabric 795 and leaving an air gap 798 in the place of the removedsacrificial layer. The inventors contemplate that the stripping of theremaining resist portions 760 and removal of sacrificial material 720may be done in the same step, with an appropriate process.

FIG. 8A, for example, is a cross-sectional view of exemplary structuresused in creating suspended, patterned nanofabrics. This method createssuspended patches of carbon nanotube fabric overlying an electrode withwhich the nanofabric may come into electrically conductive contact whenthe nanofabric is deflected. Such a device can be used as an electronicelement, e.g. as an electromechanical switch, etc.

An intermediate structure 800 is provided. Structure 800 comprises asubstrate 810 (similar to those described above) with already definedelectrodes 820 (e.g., made of sufficiently conductive material, such asdoped semiconductor or metal) and defined sacrificial material 830thereover. A nanofabric 840 covers the substrate surface and thesacrificial layer 830. The nanofabric may be made by any of theabove-described methods. Similar to that described above and asdescribed in the incorporated references, the nanofabric 840 may bepatterned (e.g., lithographic patterning) and defined portions ofnanofabric may be removed to form intermediate structure 850. Patternednanofabric articles 860 then cover defined sacrificial material 830which in turn cover electrodes 820. The sacrificial material 830 maythen be removed by selective etching, leaving remaining structuressubstantially intact, yielding structure 870. Structure 870 comprisessuspended nanofabric articles 860 separated from electrodes 820. Thenanofabric articles 860 and/or the electrodes may then be subjected toelectrical stimulus to cause the nanofabric articles 860 to deflecttoward, or away from, electrodes 820. As described in the incorporatedreferences, the deflected articles retain their deflected state in anon-volatile manner.

Example 32

A wafer substrate, an overlying nanofabric, an embedded titaniumelectrode under a sacrificial layer of Al₂O₃ are provided. Shipley 1805photoresist is applied to the wafer surface by spin coating at 4000 rpmfor 60 seconds. The photoresist is exposed using a Kasper Mask Alignerfor 8 seconds. The pattern is developed using a basic developer, therebyexposing portions of nanofabric and leaving other portions protected bythe photoresist. The substrate is rinsed in deionized water and dried at115° C. The exposed portions of nanofabric are removed by plasma ashingfor five minutes with 25 cubic feet per minute oxygen at a pressure of280 millitorr and a power of 300 Watts. The substrate is soaked inn-methylpyrollidinone at 70° C. to remove remaining photoresist for 30minutes. The substrate is rinsed in isopropanol and dried. Hotphosphoric acid is applied to remove the Al₂O₃, leaving a patternednanofabric suspended over an electrode with which it may come intoelectrical contact when deflected. FIG. 8B displays an FESEM image ofpatterned nanofabrics made by this method. In the micrograph, baresubstrate regions are dark, nanofabric patches are light in color andthe longitudinal light stripe is a metallic electrode. Typicalresistivity for a patterned trace with a length of 100 μm and width of 3μm is 1-10 MΩ. FIG. 8C displays an FESM image of the same structure asin 8B under greater magnification. The dark longitudinal stripe is thesacrificial layer overlying the metal electrode. FIG. 8D displays anFESM image of the same structure with the sacrificial layer removed; thenanofabric can be seen suspended over and not in contact with theelectrode.

Controlled Composition of Types of Nanotubes in Nanofabric

Other embodiments involve controlled composition of carbon nanotubefabrics. Specifically, methods may be employed to control the relativeamount of metallic and semiconducting nanotubes in the nanofabric. Inthis fashion, the nanofabric may be made to have a higher or lowerpercentage of metallic nanotubes relative to semiconducting nanotubes.Correspondingly, other properties of the nanofabric (e.g., resistance)will change. The control may be accomplished by direct growth, removalof undesired species, or application of purified nanotubes.

With regard to controlled direct growth, methods are known, for example,to selectively grow semiconducting nanotubes. (See Kim et al., Synthesisof Ultralong and High Percentage of Semiconducting Single-Walled CarbonNanotubes, Vol. 2 Nanoletters 703 (2002).) The inventors envision aprotocol in which selective growth of fabrics of semiconducting ormetallic nanotubes followed by etching would produce nanotube ribbons ortraces useful in fabrication of electromechanical devices.

With regard to removal of undesired species, methods are known, forexample, to process MWNTs and SWNT ropes to convert such into metallicor semidconducting nanotubes as desired. (See Collins et al.,Engineering Carbon Nanotubes and Nanotube Circuits Using ElectricalBreakdown, Vol. 292 Science 706 (2001).)

With regard to application of purified nanotubes, using proper bulknanotube preparations which contain primarily metallic or semiconductingnanotubes would allow application of a nanotube fabric to a substrate.The application could be performed via spin coating of a nanotube stocksolution onto a substrate, dipping a substrate into a nanotube stocksolution, spraying of nanotube stock solutions onto a surface or othermethods. Application of single-walled, multiwalled or mixtures of suchnanotubes can be envisioned with subsequent patterning and etching togenerate fabrics or traces of sufficient length and width to makeelectronic devices.

By way of example, FIG. 1B.2 is similar to FIG. 1B.1 and the descriptionthereof is not repeated. In material part, the method of FIG. 1B.2removes the optional step of annealing nanotubes found in FIG. 1B.1 andsubstitutes it with a selective removal of nanotubes, e.g., removingsemiconducting nanotubes or metallic. By doing so the composition of thenanofabric may be controlled.

FIGS. 3G-H is similar to FIGS. 3B-C and the descriptions thereof are notrepeated. In material part, the method of FIG. 3G adds a selectiveremoval 345 of nanotubes, e.g., removing semiconducting nanotubes ormetallic; analogously, the method of FIG. 3H adds a selective removal380 of nanotubes. By doing so the composition of the nanofabric may becontrolled.

FIG. 4C is similar to FIG. 4B and the description thereof is notrepeated. In material part, the method of FIG. 4C adds a selectiveremoval 450 of nanotubes, e.g., removing semiconducting nanotubes ormetallic. By doing so the composition of the nanofabric may becontrolled.

FIG. 4D is similar to FIG. 4B and the description thereof is notrepeated. In material part, the method of FIG. 4D substitutes the CVDstep 440 of FIG. 4B with a selective growth 440′ of nanotubes, in whichthe growth process affects the relative concentration of one type ofnanotube as compared to another. By doing so the composition of thenanofabric may be controlled.

Under some of the above embodiments, the application of nanotubes may beiterative. Thus for example a nanofabric may be created and subsequentlyprocessed to remove semiconducting nanotubes and then anotherapplication of nanotubes may be applied. Repeated application andremoval will increase the relative amount of metallic or semiconductingnanotubes in the resulting nanofabric.

FIG. 5I is similar to FIG. 5B and the description thereof is notrepeated. In material part, the method of FIG. 51 removes the optionalannealing step 540 of FIG. 5B and adds a selective removal 550 ofnanotubes, e.g., removing semiconducting nanotubes or metallic. By doingso the composition of the nanofabric may be controlled. This processstep 550 can be iterated to generate a more dense nanofabric.

FIG. 5J is similar to FIG. 5B and the description thereof is notrepeated. In material part, the method of FIG. 51 removes the optionalannealing step 540 of FIG. 5B and substitutes the dispersal step 530with a new dispersal step 530′, in which the nanotubes that are dispersehave a controlled composition, e.g., selected amounts of metallicnanotubes. By doing so the composition of the nanofabric may becontrolled. This process step 530′ can be iterated to generate a moredense nanofabric.

Other Embodiments

Catalyst deposited on substrate surface or remaining in spun-on SWNTsmay be removed by rinse/wash steps if a desired property of the ribbonincluded that it be free of metal/catalyst. This could be performed bysuccessive treatments in an appropriate solvent or acid which wouldcause the removal of the exterior carbon shell that typically passivatesthe particles during nanotube growth. Other unreacted nanoparticlescould be removed with just a mild solvent wash.

Some of the above methods of manufacturing such nanofabrics andpatterning articles therefrom are conducive to certain environments,such as a circuit manufacturing environment. Other methods providenanofabrics and articles therefrom that have desirable characteristics,such as an ability to adhere to hydrophobic surfaces (found in manyelectronic devices), even when the feature size is in the nanometerregime (<200 nm).

While the inventors typically desire a monolayer fabric of single-wallednanotubes, for certain applications it may be desirable to havemultilayer fabrics to increase current density, redundancy or othermechanical or electrical characteristics. Additionally it may bedesirable to use either a monolayer fabric or a multilayer fabriccomprising MWNTs for certain applications or a mixture of single-walledand multi-walled nanotubes. The previous methods illustrate that controlover catalyst type, catalyst distribution, surface derivitization,temperature, feedstock gas types, feedstock gas pressures and volumes,reaction time and other conditions allow growth of fabrics ofsingle-walled, multi-walled or mixed single- and multi-walled nanotubefabrics that are at the least monolayers in nature but could be thickeras desired with measurable electrical characteristics.

In the case of formation of fabrics using pre-grown nanotubes,formulation of nanotube solutions in appropriate solvents withsubsequent distribution over surfaces with or without derivitizationallows exquisite control over porosity and density of the fabrics andwould lead to facile generation of single-walled, multi-walled or mixedsingle- and multi-walled fabrics that are at the least monolayers innature but could be thicker as desired with measurable electricalcharacteristics.

It will be further appreciated that the scope of the present inventionis not limited to the above-described embodiments, but rather is definedby the appended claims, and that these claims will encompassmodifications of and improvements to what has been described.

1. A nanotube article manufactured by the following steps: applyingcarbon nanotube growth catalyst on to a surface of a substrate;subjecting the substrate to a chemical vapor deposition of acarbon-containing gas to grow a non-woven fabric of carbon nanotubes,wherein the nanotubes of the fabric are substantially parallel to saidsurface of the substrate; selectively removing portions of the non-wovenfabric according to a defined pattern; and providing first and secondelectrodes in contact with respective first and second portions of thepatterned non-woven fabric; wherein the patterned non-woven fabric formsa conductive trace between the first and second electrodes to create thenanotube article.
 2. The nanotube article of claim 1 wherein the carbonnanotube growth catalyst applied to a surface of a substrate includesmetallic nanoparticles.
 3. The nanotube article of claim 1 wherein thecarbon nanotube growth catalyst applied to a surface of a substrateincludes metal oxide nanoparticles.
 4. The nanotube article of claim 1further manufactured by a step of derivitizing the surface of thesubstrate.
 5. The nanotube article of claim 4 wherein the step ofderivitizing the surface of the substrate includes creating a morehydrophobic environment to promote adhesion of the carbon nanotubegrowth catalyst.
 6. The nanotube article of claim 4 wherein the step ofderivitizing the surface of the substrate includes creating a morehydrophilic environment to promote adhesion of the carbon nanotubegrowth catalyst.
 7. The nanotube article of claim 1 wherein the step ofapplying carbon nanotube growth catalyst on to a surface of a substrateincludes applying a ferritin solution.
 8. The nanotube article of claim1 wherein the carbon nanotube growth catalyst creates a substantialmonolayer of nanoparticles on the surface of the substrate.
 9. Thenanotube article of claim 1 wherein the step of applying carbon nanotubegrowth catalyst on to a surface of a substrate includes applying a metalligand-catalyst precursor.
 10. The nanotube article of claim 9 whereinthe surface is functionalized to promote binding of the ligand.
 11. Thenanotube article of claim 9 wherein the metal ligand-catalyst precursorhas a formula ML, in which M is metal from a group including iron,cobalt, or nickel, and in which L is at least one organic ligand. 12.The nanotube article of claim 9 wherein the metal ligand-catalystprecursor is applied by a spin coating technique.
 13. The nanotubearticle of claim 9 in which the metal ligand-catalyst precursor isoxidized to remove an organic shell therefrom.
 14. The nanotube articleof claim 1 wherein the step of applying carbon nanotube growth catalyston to a surface of a substrate includes applying a solution of ironoxide nanoparticles on the surface of the substrate.
 15. The nanotubearticle of claim 14 wherein a spin coating technique is used to applythe solution of iron oxide.
 16. The nanotube article of claim 15 whereinthe spin coating technique includes repetitive applications of thesolution of iron oxide nanoparticles and repetitive distributing thereofby spinning the substrate at a defined rate.
 17. The nanotube article ofclaim 1 wherein the step of applying carbon nanotube growth catalyst onto a surface of a substrate includes applying a suspension of liquidmetal catalyst precursor on the surface of the substrate.
 18. Thenanotube article of claim 1 wherein the carbon-containing gas comprisesmethane.
 19. The nanotube article of claim 1 wherein thecarbon-containing gas comprises ethylene.
 20. The nanotube article ofclaim 18 wherein chemical vapor deposition is at about 850° C. for aboutten minutes and the methane is applied at about a 500 sccm flow.
 21. Thenanotube article of claim 19 wherein chemical vapor deposition is atabout 800° C. for about forty minutes and the ethylene is applied atabout a 10 sccm flow.
 22. The nanotube article of claim 1 wherein thestep of subjecting the substrate to chemical vapor deposition includessubjecting the substrate to inert gasses.
 23. The nanotube article ofclaim 22 wherein the inert gasses comprise a controlled flow of Argonand Hydrogen.
 24. The nanotube article of claim 23 wherein thecontrolled flow of Argon and Hydrogen comprises a flow ratio of 1:4. 25.The nanotube article of claim 1 further manufactured by a step ofoxidizing the substrate prior to chemical vapor deposition.
 26. Thenanotube article of claim 1 wherein the nanotube growth catalystscomprise nanoparticles having selected diameters.
 27. The nanotubearticle of claim 1 wherein the carbon nanotubes of the non-woven fabricinclude metallic nanotubes and semiconducting nanotubes and wherein therelative composition of metallic and semiconducting nanotubes in thefabric is controlled.
 28. The nanotube article of claim 1 wherein thecarbon nanotubes of the non-woven fabric include metallic nanotubes andsemiconducting nanotubes and wherein the manufacturing steps furtherincludes selectively removing metallic nanotubes.
 29. The nanotubearticle of claim 1 wherein the carbon nanotubes of the non-woven fabricinclude metallic nanotubes and semiconducting nanotubes and wherein themanufacturing steps further includes selectively removing semiconductingnanotubes.